Authors:W. Ciesińska, J. Zieliński and T. Brzozowska
Coal-tar pitch was modified by addition of polystyrene, poly(ethylene terephthalate), unsaturated polyester and coumarone-indene
resin. The optimum conditions for production of homogeneous binary pitch-polymer blends containing 10% w/w of the polymer were established. Softening points, contents of toluene and quinoline-insoluble matters and rheological properties
of the blends were determined. The yield of solid fraction in semi-coking the blends was also found. The effect of polymers
on the coal-tar pitch blend properties was evaluated. Some pitch-polymer blends were then carbonized to carbon sorbents used
for purification of water and wastewater.
Thermal analysis and polymers are two subjects in the field of chemistry and materials sciences that have not developed to the level commensurate with their importance. In this paper the reasons for this deficiency are traced to the history of the development of these subjects which led to only limited availability of courses of instruction. A first remedy to this problem is suggested, teaching via the internet. The attempt by the author to generate such a course is described in this paper. The course contains an up-to-date store of basic information. It is divided into 36 lectures and displayed in about 3000 computer screens filled with graphs, text, and hypertext. All lectures are downloadable. Including presentation software, each lecture requires only 1–3 Mbyte of computer memory. The inclusion of color,movies, and sound would exceed the capacity of most presently available personal computers,but might point the way to future of teaching the ever increasing number of subjects.
The thermal degradation of polymers has been studied quite extensively using thermogravimetric measurements. For the kinetic
description, most of the times single rate heating data and model-fitting methods have been used. Since the thermal degradation
of the polymers is a very complex reaction, the choice of a reliable model or a combination of kinetic models is very important.
The advantages or the disadvantages of using a single heating rate or multiple heating rates data for the determination of
the kinetic triplet have been investigated. Also, the activation energy has been calculated with the isoconversional and model-fitting
methods. The reaction model was determined with the model-fitting method. The limits of all these procedures were investigated
with experimental data of the thermal degradation of the poly(ethylene adipate) (PEAd).
Differential Scanning Calorimetry is frequently used for measurements of thermal properties on all kinds of substances. The
temperature lag in the samples depend on the thermal properties and the thermal contact between sample and sample holder.
In the paper, we discuss the temperature distribution in samples of comparatively low thermal conductivity, such as polymers.
The purpose of this study is to pinpoint the substantial temperature differences that may occur in such bad conducting samples
under different conditions. The calculations of the temperature gradients have been carried out by using a finite element
Intense parasitic nucleation has been observed at the surface of differential scanning calorimetry samples for various polymers,
whereas their crystallization traces exhibit complex shapes. Revisited overall kinetics theories and computer simulation,
taking into account small thickness of samples and transcrystallinity effects, allow to explain and reproduce experimental
‘double peaks’, currently observed with polyamide 6-6. The beginning of the transformation and the main peak are attributed
to surface and bulk nucleations, respectively. As a consequence, any DSC experiment should be followed by a microscopic observation
and more accurate models including thermal gradients and resistances should be developed for their interpretation.
Polymer characterization has largely helped in the development of thermal analyzers and calorimeters, based mainly on the thermocouple technology, or more recently the semiconductor technology. With the use of an integrated silicon thermopile as a detector, a new thermal technique is appearing, to give more possibilities of investigations in the field of polymeric materials. Combining high sensitivity and use of small amount of sample, the originality of the new design comes from its low power consumption, giving rise to a portable version of the instrument. With such a concept, the thermal analysis technique is carried on the industrial site, to perform online measurements.Melting and crystallization, glass transition, control of reticulation are a promising field of applications for the characterization of polymeric materials on industrial sites.
This study aims to develop and validate a high-performance size-exclusion chromatography (HPSEC) method to determine the amount of polymer in cefmetazole sodium for injection and to compare this method with gel chromatography. A Zenix SEC-150 column was used with the mobile phase of phosphate buffer solution (pH 7.0; 0.01 M)—acetonitrile (90:10 v/v) at a flow rate of 0.8 mL min−1 and a detection wavelength of 240 nm. The polymer was quantified by an external standard method with self-control, and the amount was expressed by the percentage of cefmetazole. The HPSEC method was validated for specificity, linearity, and precision. The chromatographic conditions, chromatographic performances, sensitivity, linearity, and precision of the developed HPSEC method and gel chromatography were compared, and both methods were subsequently used to determine the amount of polymer from seven batches of samples. The HPSEC method was fully validated. The time of isocratic elution for sample assay was less than 14 min. The results of comparison indicate that the developed HPSEC method was superior to gel chromatography. The Student t test results also showed significant difference in the amount of polymer from the samples obtained by the two methods. Thus, the HPSEC method with two obvious advantages, the superior sensitivity and a shorter analysis time, is more suitable for determination of polymer amount in cefmetazole sodium for injection to control the quality of the product.
Authors:C. Bacharan, C. Dessaux, A. Bernès and C. Lacabanne
Thermally Stimulated Current (TSC) spectrometry has been applied to the characterization of polymeric materials. The study
of a series of amorphous polymers having different physical structures has shown that the compensation parameters are independent
of physical aging; contrarily, the activation enthalpy distribution reflects the evolution of the heterogeneity of the amorphous
In copolymers, TSC allows us to identify segregated amorphous phases. In semi-crystalline polymers, with semi-rigid chains,
we have shown the existence of an amorphous crystalline interphase characterized by a plateau in the temperature distribution
of activation enthalpy.
Authors:C. Schick, M. Merzlyakov, A. Minakov and A. Wurm
Quasi-isothermal temperature modulated DSC (TMDSC) were performed during crystallization to determine heat capacity as function of time and frequency. Non-reversible and reversible phenomena in the crystallization region of polymers were distinguished. TMDSC yields new information about the dynamics of local processes at the surface of polymer crystals, like reversible melting. The fraction of material involved in reversible melting, which is established during main crystallization, keeps constant during secondary crystallization for polycaprolactone (PCL). This shows that also after long crystallization times the surfaces of the individual crystallites are in equilibrium with the surrounding melt. Simply speaking, polymer crystals are living crystals. A strong frequency dependence of complex heat capacity can be observed during and after crystallization of polymers.
Temperature modulated differential scanning calorimetry (TMDSC), the most recent development that adds periodic modulation to the conventional DSC, has recently seen a fast growth due to availability of commercial instrumentation. The use of the technique necessitates a total control of all of the experimental parameters. The paper focuses on recent applications to investigate polymers .